CS331891A3 - Film-forming or foil-shaped material comprising crystalline polypropylene polymeric mass - Google Patents

Abstract

Disclosed is a film or sheet material comprising a blend of (1) a crystalline propylene polymer composition which is comprised of, by weight, (A) from about 30 to 65% of a copolymer of propylene with a C4-8 alpha-olefin containing from 80 to 98% propylene, and (B) 35-70% of a co- or terpolymer of propylene with ethylene and, optionally, a C4-8 alpha-olefin having an ethylene content of 5 to 10% when ethylene is the sole comonomer and an ethylene content of 0.5 to 5% and a C4-8 alpha-olefin content of 1 to 9.5% when both ethylene and a C4-8 alpha-olefin are used as comonomers, and (2) an olefin polymer.

Description

, C 1 - C 1-1 j; N ·

i I

Film or sheet material containing crystalline propylene polymer mass

Technical field

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a weldable mass based on propylene polymer in the form of films or sheets, laminates formed therefrom, and coextruded materials.

BACKGROUND OF THE INVENTION In many film applications, for example as packaging materials for food, chemicals and hazardous materials, and for medical use, industry requires films with certain properties. in the case of food packaging, the films must have high puncture resistance, high clarity and gloss, reduced permeability to gases and / or vapors and good weld strength; films used for the manufacture of chemical containers and hazardous waste materials must have high puncture resistance, high ductility, high tear resistance, high chemical resistance, and good weld strength; films for medical use, for example, for blood bags, must have high puncture resistance, low modulus, high tear resistance, autoclavability and good weld strength.

Films made from ethylene polymers such as HDPEa LLDPE and propylene polymers such as crystalline propylene homopolymers and random propylene copolymers. ethylene, do not exhibit such a combination of desirable properties.

Crystalline statistical propylene copolymers and ethylene are often used for the preparation of such films, for the inherent clarity of such copolymers. However, films prepared from crystalline propylene copolymers and less than 3% ethylene or mixtures thereof with other olefin polymers do not exhibit good welds or weld strengths, since the melting point of these copolymers or mixtures thereof is too close to that of the base polymer layer on them or simultaneously with them, which is typical of the crystalline propylene homopolymer. The resulting laminate or coextruded material does not have dimensional integrity or stability.

When making films from a crystalline propylene-ethylene random copolymer containing about 5 to 6% ethylene, the melting point of such a copolymer is reduced to the melting point of the crystalline propylene homopolymer, such that the copolymer film does not exhibit some weldability characteristics. However, incorporation of the monomer disrupts the crystalline structure with the concomitant formation of an increased amount of xylene soluble polymer at room temperature. Therefore, the mechanical properties of films formed from such copolymers are adversely affected. In addition, the content of the large amount of xylene soluble fraction imparts the sensitivity to the film to the organic matter and is thus unsuitable for food packaging. Films prepared from mixtures of such crystalline. copolymers of propylene with other polymers do not exclude these disadvantages.

Accordingly, there is a need for a material for films or low-temperature welding initiating temperatures, as well as other desirable properties comprising a propylene polymer material having a low xylene soluble polymer fraction at room temperature and weldability. In the following, all parts and percentages are by weight, unless otherwise indicated, and all temperatures are as follows, with room temperature being 25 ° C.

SUMMARY OF THE INVENTION

The substance of the crystalline propylene polymer film or sheet composition according to the invention is that it contains about 30 to 65% by weight of a propylene copolymer of 4 to 8 carbon atoms containing 80 to 98% -3 propylene and / or B / 35 to 70% propylene copolymer or terpolymer with ethylene and optionally 4 to 8 carbon atom-olefins and ethylene content 5 to 10% when ethylene is a single monomer and an ethylene content of 0.5 to 5% and an alpha olefin with 4 to 8 carbon atoms, when both ethylene and 4 to 8 carbon alpha-olefins are used as comonomers, with a total comonomer content of 2 to 10%. The total content of (A) and (B) is 100

Vynálea. also relates to films or sheets comprising a layer of propylene polymer deposited on at least one surface-thermoplastic film material or metal substrate.

The invention also relates to films or sheets of mixtures of propylene polymer and thermoplastic polymeric material.

The component (A) is preferably present in an amount of 35 to 65%, in particular in an amount of 45 to 65%. The propylene content of the component (A) is preferably 85 to 95%. % and especially in the amount of 35 to 55% · If the component is / B / terpolymer, the total comonomer content, that is ethylene and the alpha-olefin with 4 to 8 carbon atoms, is 2 to 10 and preferably 3 to 6% and the ethylene content is preferably 1 to 3 If the component (B) is a copolymer, ethylene is preferably present in an amount of 7 to 9%.

C 4 to C 8 alpha-olefins, suitable for the preparation of propylene polymer components, include pentene-1, pentene-1, hexene-1,4-methylpentene-1 and octene-1. Especially preferred is butene-1. Preferred films are those prepared from a propylene polymer in which there is no C 4 to C 8 alpha-olefin in the ZB component.

The propylene polymer composition useful for preparing film and sheet according to the invention has a melting point of about 125 to 14 ° C, a polymeric fraction soluble in xylene at ambient temperature, less than 20% by weight, preferably less than 15% by weight, and more preferably less than 20% by weight. 10% avn-hexane soluble polymer fraction less than 5.5% at 50 ° C. Films or sheets made of such masses have a starting welding temperature, (further defined) of 100 to 110 ° C. The initial temperature of the weld or the temperature initiating weld (SIT) is the minimum temperature at which a weld is formed in the case of a multi-layer film having a polypropylene film layer and an affil layer of the propylene polymer mass of the invention, wherein the weld must not break up under the load of multi-layer film 300 g. This requirement will be explained in more detail in the examples.

The propylene polymer compositions useful for making the alist films of the invention are prepared by sequential polymerization of the respective monomers in the presence of a stereospecific Ziegler-Natta catalyst system comprising a solid catalyst component supported by a magnesium halide in active form. It is important that such a solid catalyst component contain a titanium compound having at least one halogen-titanium bond and an electron donor compound carried on the magnesium halide in the active form. Such a catalytic system, useful in the preparation of a propylene polymer mass, is characterized by the fact that it produces polypropylene with an isotactic index higher than 90%, preferably greater than 95% under optimum conditions. Catalyst systems having such characteristics are well known in the patent literature. Particularly preferred are the catalyst systems described in U.S. Pat. Nos. 4,339,554, 4,425,224 and 4,476,606 and European Patent Specification No. 45977.

The solid catalyst components used in these catalyst systems include, as electron donor compounds, ethers, ketones, lactone compounds containing nitrogen, phosphorus, and / or sulfur atoms, and monocarboxylic and dicarboxylic esters. acids. Particularly useful as electron donor compounds are phthalic acid esters such as diisobutyl phthalate, dioctyl phthalate and diphenyl phthalate and benzyl butyl phthalate; malonic acid esters such as diisobutyl malonate and diethyl malonate; alkyl maleates; alkyl carbonates and aryl carbonates such as diisobutyl carbonate, ethyl phenyl carbonate and dienyl carbonate; and succinic acid esters such as monoethylsuccinate and diethylsuccinate.

Other, particularly preferred, ether electron donor compounds are those of the general formula

I where R and R, which are an alkyl group having 1 to 1

IX

X

GH 8 OR 11 G 11 OR 17 are identical or different from each other, meaning 18 straight or branched carbon atoms, a cycloalkyl group and 5 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, R 11 1 and R 17, which are the same or each other different, alkyl and 1 to 4 carbon atoms and straight or branched chain. Typical esters of this type and methods for their preparation are described in U.S. Patent 4,111,039, filed Sep. 27, 1989, in U.S. Patent No. 2-Methyl-2-isopropyl-1,3-dimethoxypropane. 2,2-diisobutyl-1,3-dimethoxypropane and 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane.

The supported catalyst component can be milled. a conventional anhydrous magnesium halide, that is, a non-activated magnesium halide containing less than 1% water, a titanium compound and an electron donor compound, which results in activation of the magnesium halide. The milky product is then treated once or several times with excess titanium tetrachloride at 90 to 135 and repeatedly washed with a hydrocarbon (e.g., hexane) to remove all of the chlorine in the wash liquid.

Alternatively, the anhydrous magnesium halide is pre-activated by known methods and then treated with an excess of titanium tetrachloride containing an electron donor compound in solution at 80-135 ° C. Titanium tetrachloride treatment was then performed. and the solid mass is then washed with hexane or another suitable node to remove any traces of unreacted titanium tetrachloride. The magnesium halide compound or complex thereof may be formed in addition from a magnesium compound capable of forming a halide halide containing titanium compound, preferably titanium tetrachloride.

In another method, the supported solid catalyst can be prepared by forming an adduct, preferably in the form of spherical particles, magnesium chloride and an alcohol such as ethanol, propanol, butanol, isobutanol and 2-ethylhexanol, the molar ratio being 1: 1 to 1: 3, which is then treated with an excess of titanium tetrachloride containing an electron donor compound in solution. The temperature in this process is generally 80-120 ° C. The solid is recovered and treated again with thionium chloride. The solid was separated and washed with a hydrocarbon solvent until the chlorine ions disappeared from the wash solvent.

According to yet another method, the alkoxy magnesium compound and the alkoxy magnesium chloride compound (wherein the alkoxy magnesium chloride compound is prepared by the process of U.S. Pat. No. 4,220,554) is treated with excess titanium tetrachloride containing electron donor compound under the above reaction conditions. conditions.

The solid catalyst component, the titanium compound, expressed as titanium, is generally present in an amount of from 0.5 to 10, and the amount of electron donor compound fixed to the solid / internal donor is generally about 5 to 20% with respect to the magnesium halide. As useful titanium compounds for the preparation of the solid catalyst component, titanium halides and alkoxy halides are mentioned. The preferred compound is titanium tetrachloride. Titanium (III) halides and titanium alkoxyhalides, such as TiCl2 OR, where R is phenyl are also satisfactory.

In addition to the above-mentioned reactions which lead to the formation of magnesium halide in active form, other reactions are known from the literature which lead to the formation of magnesium halide in active form from magnesium compounds other than halides such as, for example, alkoxy magnesium compounds and magnesium carbonate.

The active form of the magnesium halide in the solid catalyst component is evidenced by the X-ray spectrum of the solid catalyst component by the absence of a high intensity diffraction line which is in the X-ray spectrum of the non-activated magnesium halide (less than 3 m / g), but instead is the maximum intensity shifted with respect to the position of the diffraction line and the high intensity of the non-activated magnesium halide, or the active form is evidenced by the fact that the high intensity diffraction line has an extension having half peak widths of at least 30% greater than the diffraction line width of the inactivated magnesium halide ·. The most active are the forms in which the aforementioned halogen appears in the X-ray spectral catalyst component.

Magnesium chloride is the preferred compound. In the case of the most active forms of magnesium chloride, the X-ray spectrum of the solid catalyst component exhibits halogen instead of the diffraction pattern which appears in the X-ray spectrum of the non-activated magnesium chloride at a distance of 0.156 nm.

Aluminum alkyl compounds useful as octocylsators include aluminum trialkyls such as aluminum triethyl, aluminum triisopropyl, and aluminum triisobutyl aluminum dihydric alkylsides having from 1 to 6 carbon atoms in the alkyl moiety, such as aluminum diethyl hydride and compounds containing two or more aluminum atoms with each other. it is bonded via an oxygen, nitrogen and / or sulfur atom, such as, for example, the compounds vzoreex (CgHj / gA1-O-Al / CgH2O) (Al2O-Al-Al / Cl2 / g, Al-O-). n,

(C 8 H 11 / gAl-O-S-O 2 Al / C 2 / g, CH.0)

wherein n is 1 to 20. The preferred aluminum alkyl compound is aluminum triethyl (TEAL).

In addition, compounds of the general formula wherein R * is an aryl group substituted in one or two positions by an alkyl group of 1 to 6 carbon atoms and R is an alkyl group of 1 to 6 carbon atoms can also be used.

The aluminum alkyl compounds are generally used in such an amount that the aluminum / titanium ratio is 1 to 1000 ·

Electron donor compounds which can be used as electron donors with an aluminum alkyl cocatalyst compound include esters of aromatic acids such as, for example, alkyl benzoates and organosilane compounds. Typical organosilane compounds are those having Si-OR, Si-OCOR or Si-NRg bonds, wherein R is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, These compounds are described, for example, in U.S. Pat. Nos. 4,472,224, 4,529,230, and C20, C20-C20 aryl or C5-C20 cycloalkyl. Suitable organosilane compounds include the compounds of the formula: t-butyl (OCH 2) 2, cyclohexyl (SiS) OCH 2 / (g), 4, 577, 486, 45976 and 45976 and 45977, respectively. It is also preferable to use the 1,3-diethers of the above formulas. If the internal donor is one of these diethers, the external donor may be absent.

IN

The polymerization of the respective monomers is carried out in at least two stages, so that the components (A) and (B) are prepared in separate stages, in each successive stage the polymer and the catalyst used in the previous stage, i.e. it does not add any additional catalyst to the second stage.

For example, the component (B) may be prepared in one step and the component (A) in the next step. The sequence according to which the components (A) and (B) are prepared is not critical.

The polymerization reaction may be carried out intermittently or continuously by methods known per se and carried out under inert atmosphere by the presence of a liquid or gaseous monomer or mixtures thereof. and optionally in the presence of an inert hydrocarbon solvent, at a temperature of generally about 20 ° C to about 100 ° C, preferably 50 to 80 ° C, and under pressure generally from ambient pressure to 7.0 MPa, preferably 1.4 to 1.5 bar. 3.5 MPa in liquid phase polymerization and generally at ambient pressure up to 4.20 MPa in gas phase polymerization. Gas phase polymerization is preferred. The delay time is approximately 15 minutes to 6 hours. Hydrogen may be added as necessary as a chain transfer agent to enhance the molecular weight of the polymer.

The catalysts may be pre-contacted with small amounts of the corresponding olefin monomer (prepolymerization) while maintaining the catalyst in suspension in the hydrocarbon solvent, wherein the polymerization is carried out at 60 ° C or at a lower temperature for a time sufficient to produce the polymer; in an amount of 0.5 to 3 times by weight of catalase. The prepolymerization can also be carried out in a liquid or gaseous monomer to produce in this case a polymer up to 1000 times with respect to the weight of the catalyst.

Since the components (A) and (B) are prepared directly in the polymerization, the resulting propylene polymer in the form of polymerized particles in such particles is the components (A) and (B) optimally mixed so that the resulting propylene polymer mass is it is directly usable for making films without performing a polymerization treatment such as granulation. Preferred propylene polymer compositions are in the form of spherical or spherical particles having a diameter of 0.5 to 4.5 mm, and in particular with a granulometric distribution, wherein at least 90% of the particles are 0.5 to 3.5 mm in diameter. lacquer particles are obtained, for example, using the catalyst systems described in U.S. Patent No. 4,473,224.

The solid catalyst component is prepared as follows: A / Preparation of magnesium chloride adduct and alcohol In another atmosphere, 48 g of anhydrous magnesium chloride, 77 g of anhydrous ethyl alcohol and 830 ml of kerosene are heated to room temperature, into a 2 liter heated vessel, with a turbine-driven stirrer and a drain pipe. The components are then heated to 120 ° C with stirring to form a magnesium chloride adduct and an alcohol adduct and mix with the dispersant. A nitrogen pressure of 1.5 MPa is maintained in the vessel. The vessel outlet pipe is externally heated to 120 ° C with a heating sleeve. The outlet pipe has an inner diameter of 1 mm and a length of 3 a, guided by a heating sleeve. The tube-free mix at a rate of approximately 7 m / s. At the outlet of the tube, the sediment is introduced into a 5 liter vessel equipped with a stirrer containing 2.5 liters of kerosene, and the vessel is externally cooled in a vessel where the initial temperature of -40 is maintained. The temperature of the emulsion discharged from the vessel is 0 ° C. The spherical solid product forms the dispersion phase of the emulsion and is separated by decantation and filtration, washing with heptane and drying. All of the above operations are carried out in an inert gas environment.

This gives the compound of formula HgCl2. 3 CgH3 OH (130 g) as solid spherical particles with a maximum diameter of less than 50 microns. The solid product, after drying in a vacuum for two hours, weighs 105 g. The solid product is then heated under nitrogen and maintained at a temperature of about 60 ° C to partially dealcoholize the spherical adduct particles to a sufficient extent to reduce the adduct alcohol content by about one third. The adduct obtained has the formula

MgCl 2. 2.1 Cl2 OH B Preparation of a solid catalyst component

To a 1 liter glass flask equipped with a condenser, a mechanical stirrer and a thermometer, 625 ml of TiCl4 were introduced in an anhydrous nitrogen atmosphere, and 20 g of adduct of the formula was introduced into the flask at 0 ° C.

MgCl 2. 2.1

The components are heated to 100 ° C for one hour.

When a temperature of 40 ° C is reached, 9 mmol of diisobutyl phthalate are introduced. The reaction mixture was maintained at 100 ° C for two hours. and allow to settle. • The supernatant liquid is withdrawn. Titanium tetrachloride (550 mL) was added to the solid and maintained at 120 ° C for one hour. The reaction mixture was allowed to settle and the supernatant was withdrawn. The solid residue is washed with 200 ml each of anhydrous hexane at 6 DEG C. for 3 times at room temperature.

The process of the invention and the invention are explained in more detail by the following non-limiting examples. Examples 1 and 2

These examples illustrate the propylene polymer mass and its method of preparation. Preparations for polymerization and polymerization processes are carried out in a nitrogen environment, in a series of reactors with means for converting the formed product Ivr immediately preceding; reactor to the next reactor. All temperatures, pressures and concentrations of olefinic monomers and optionally hydrogen are kept constant unless otherwise indicated. The concentration of hydrogen and the corresponding monomers is continuously analyzed in the gas phase gas. brnmat.ngraphy to maintain a constant concentration.

According to the examples, the electron donor TEAL activator of adicyclohexyldimethoxysilane is contacted in such a quantity that the TEAL: silane weight ratio is about 6.5, with such a solid catalyst component that the TEAL: Ti molar ratio is about 65, at 5 ° C in the reactor. The catalyst is then transferred to another reactor containing excess liquid propylene and propylene is prepolymerized for 3 minutes at 20 ° C. In the first step, the prepolymer is transferred to another reactor. for gas phase polymerization of the respective monomers to give fraction (B) according to Example 1 and fraction (A) according to Example 2 »

In the second stage, the product from the immediately preceding reactor is fed to the second gas phase reactor after degassing the unreacted monomers to form the other two components (A) or (B). At the end of the second stage of polymerization, the product is introduced into the brewing unit and the unreacted monomers are removed and the volatiles removed by a 105 ° G processing apparatus at ambient pressure for about 10 minutes and then dried.

The components and the respective working conditions are given in Table 1 and the test results of the respective components (A) and (B) and the final propylene polymer mass are given in Table 1B.

With respect to Table 1B, the following analytical methods are used:

Method I, spectroscopy. spektroskopieDSd

ASTM DM: 238, condition L determined in tetrahydron

the talen at 135 ° C was determined by dissolving the sample in xylene at 125 ° C and cooling to room temperature; the soluble and insoluble fraction was separated by filtration of a 10 µm micron film and extracted with n-hexane at 50 ° C for 2 hours, then the hexane was evaporated and the dry residue was decanted.

Ethylene property,% w / w butene-1,% w / w melting temperature, intrinsic viscosity / I.V./ fraction xylene soluble,% w / w hexane fraction,% w 12a

Table IA Examples 1 2 First gas phase reactor temperature, ° C 65 65 pressure, MPa 1.7 1.7 dwell time, min 75 75 Hg / C ^, mol% 0.003 0.035 mol% 0.151 - ^ 2 ^ 2 + C3 '11101 0.023 - G-4 / C4 + Οβ, mol% 0.044 0.178 Gas phase reactor, temperature, ° C 70 70 pressure * MPa 1.7 2.0 dwell time, min 45 45 Hg / Cp mol% 0.005 0.025 1 ^ / ¾, mol% - 0,505 ^ / C2 + C, mol% '- 0,041 C ^ / C ^ + C, mol% 0,214 - 13

Table 1B Examples 1 2 fraction / A /,% 52.0 45.1 / & /,% 48.0 54.9 ethylene in / B /,% 2.5 3.8 butene-1 in / A /, % 14.2 15.3 butene-1 v / B /,% 3.6 - melting point + - 132.8 mil +, g / 10 min 1.65 6.07 IV +, dl / g 2.31 1, 69 xylene soluble fraction at 25 ° C,% 15.72 11.72 IV xylene soluble fraction, dl / g 1.78 1.02 hexane soluble fraction at 50 ° C,% 3.0 5.0 g polymer yield + 6500.0 20000.0 g catalyst component + final propylene polymer mass per cent in table they are always meant by weight

The weld initiation temperature (SII / propylene polymer mass according to Examples 1 and 2) is determined by extruding the masses at a temperature of about 200 ° C to a 50 micron film thickness. a film layer of polypropylene having an isotactic index of 97 and a melt index of 4.5 g / 10 min. The loaded film layer is treated in a plate press at 200 DEG C. under a pressure of 9000 kg for 5 minutes to form a lamina. The two laminates are stretched to 6 times their height in the machine and crosswise using a TM Long unit to provide a laminated film of about 29 microns. From these biaxially oriented laminated films, test pieces of 5x10 cm are cut out »

The two test pieces mentioned above from each mass are laid with layers made of the propylene polymer mass of Examples 1 and 2 facing each other. The applied films are then boiled over a length of 5 cm using a Sentinel CombinationLaboratory, Model 12-12AS.TM. weld 2,5 cm. The temperature of each measured sample increases by 2 ° C. The best bonded or welded samples are then cut to obtain 2.5 x 10 cm strips and suspended in the dynamometer to unbroken sample ends. NETWORK. there is such a temperature at which the joint or weld does not break when using a load of 300 g as described above. NETWORK. the propylene polymer composition of Examples 1 and 2 is 100 and 105 ° C. Example 3

This example illustrates the air-cooled blown material film containing propylene polymer mass and its method of preparation.

Air-cooled, blown film r from the propylene polymer mass of Example 2, stabilized with 0.025 parts per 100 parts of propylene polymer mass (pph / octadecyl-3,5-bis- (1,1-dimethylethyl) -4-hydroxybenzenepropanoate, 0.075 pphtetra-racium) thylene / 3,5-di-tert-butyl-4-oxyhydroxybutamate / 7-methane, 0.08 pph of Sandostab P-EPQ, the main component of which is tetrakxs / 2,4-di-tert, -butylphenyl / -4,4 * -biphenylendiphosphonite and 0.05 pph. calcium stearate, and to which 0.15 pM Millad 3905 is added, a dispensed mass is prepared into a single-screw extruder and extruded through a round nozzle and blow molded to form a film using a sufficient amount of air to form a 0.025 mm film using the following equipment and working conditions: snail. compression ratio 3: 1 to 4: 1; polyolefin barrier type L / D ratio 24: 1 to 30: 1; blow ratio 2.5 to 4.1; nozzle gap 1.016 mm for thickness 0.0127 mm to 0.127 mm extruder profile 193 to 221 ° C from zone 1 to zone 6

adapter and nozzle temperature 232 ° G with the exception of the upper and lower nozzle zone, which is 238 C screw speed speed 20 / min pressure 21.0 MPa

The properties of the obtained film are shown in the following Table II - 15 -

Table II

Resins. c e

Property. Example 2 HDPE1 LLDPE2 Yield Strength. / MD / CD3 /, MPa 24.02 / 24.23 26.30 / 22.02 12.24 / 12.17 Tensile Strength / MD / CD /, MPa 24.02 / 24.23 27.72 / 22 , 51 14,64 / 13,29 Relative extension / MD / CD /,% 11/12 30/7 80/17 in creep

Relative elongation at break / MD / CD /,% 112/172 120/350 317/425

Burst Elemenorph / MD / CD / g / ply 8/10

Burst Irou-

seir / MD / CD / 206 / 32Q 4.8

Gloss 72

Friction coefficient 10/282 350/790 147/1026 76,8 10 503/758 8,7 70 / static ký- / kine t ic «* / 1,08 / 0,70

Water-permeability throughput at 38 ° C and 100% relative humidity / 645 crn ^ / 24 h 0.987 0.241 / 0.192 0.688 / 0.650 1.300

Cutting-edge treatment 0,12 0,55 0,79 2 quantity LR 732 HDPE with density 0,953 g / cnr

Dowlex 2045 LLDPE containing hexene-1 and having a density of 0.920 g / cm 3 3 MD / CD = longitudinal direction / transverse direction From Table II, it is clear that the propylene polymer mass of the invention produces an air-cooled blown film having a less haze, better gloss, improved barrier characteristics with regard to moisture and better overall balance of properties. In addition, it is recalled that propylene polymer material, the largest proportion of which is propylene units, generally causes less difficulty, if at all, causing difficulties in air-cooled blown film devices. Example 4

This example illustrates the cast film material containing propylene polymer mass and the extruded film of propylene polymer mass and homopolymer propellant and their method of preparation.

The cast film of the propylene polymer mass according to Example 2, stabilized as in Example 3 but without nucleationMillard 3905, and a cast film of equally stabilized propylene polymer with the addition of 0.15 pph Nucler 3905 / N /, was prepared by feeding each component into an extruder and by extrusion through a flat film nozzle and cooling on a cooling cylinder to produce a film having a thickness of 0.0254 mm. using the following equipment and working conditions of the screw construction: compression ratio 4: 1 to 3: 1 filling zone sponge: 11.05 mm to í 45i ® mm / 88.9 mm extruder with a compression ratio of 3.5: 1 / depth dosing zones: 3.18 mm to 3.56 mm for 88.9 mm extruder nozzle: conventional, centrally filled extruder working conditions: melt temperature 221-260 ° C;

extruder profile 177 to 216 ° C from zone 1 to zone 6 of adapter and nozzle 216 ° C

A coextruded film having a thickness of 30.032 mm of the propylene polymer composition of Example 2, stabilized both of Example 3 and free of Milad 3905 and homopolymerupropylene Pro-PC PC 942 with a melt flow rate (MFR) of 6.0 dg / min is prepared by a film casting technique. The properties of the obtained film are shown in the following table lilo 17

labuka III P Property Example 2 line Example 2 + Coex ^ PE Co2 A 15.64 / 14.85 21.07 / 19.86 19.50 / 18.45 17.66 / 17.16 B 48.31 / 23.71 45.09 / 44 ^ 22 36.78 / 24.64 28.84 / 23.54 G 16/13 16/17 10/9 15/10 D 571/595 520/523 '522/590 522 / 584 E 44/1019 19/985 51/132 49/102 Haze 1.3 3.2 2.8 2.3 Gloss 86.7 80.4 85.0 78.1 E No slip 1.44 / 1.03 0.463 / 0.30 0.291 / 0.213 G 0.226 0.200 0.152 0.207 G at 37.8 ° C 0.923 0.887 0.682 0.923 1 propylene polymer mass according to Example 2 / propylene homopolymer / propylene polymer mass according to Example 2 propylene ethylene random copolymer ethylene3.0% 3 MD / GD = longitudinal / transverse direction

In the column "property · *, the individual letters have the following meaning: A = yield strength / MD / CD /, MpaB = tensile strength / MD / GD /, MPaC = elongation / MD / CD /,% at creep. D = relative elongation at break / MD / CD /,% E = burst, Elemendorf / MD / CD / g / plyE - friction coefficient / static / kinetic / G = water vapor permeability at 23 ° C and 90¾ relative humidity g / 645 cm.3 / 24 h From Table III it is clear that the polymeric propylene composition of the invention provides a higher strength cast film, with improved yield strength, with less haze in the absence of nucleating agent, with improved moisture barrier properties and improved overall balanced features »16 Example 5

This example illustrates a biaxially oriented film material containing propylene polymer mass and a co-extruded film of propylene polymer mass and homopolymer polypropylene and a process for their preparation.

The biaxially oriented film of the propylene polymer mass of Example 2, stabilized as in Example 3 but without the Millad 3905 nucleation, is prepared by dispensing the components into the extruder and extruding them through a slit nozzle and cooling the sheet formed. The sheet is then oriented in a longitudinal direction between the rollers running at different speeds and then in a drying and tensioning frame for transverse orientation through diverging chain chains when the biaxial orientation is terminated. with the cooling of the film. A film thickness of 0.0254 mm is obtained. The following equipment and working conditions are used:

Extrusion Profile: Zone I Zone I 210 ° C Zone 2 216 ° C Zone 3 221 ° C Filter 221 ° S Adapters 1 and 2 221 ° C Nozzle Zone 1 227 ° σ Zone 2 and 3 227 ° C Cooling Cylinder 30 ° C MDO zone 1 63 ec MDO zone 8 88 ° c zone 1 and 2 143 ° c zone 3 130 ° c zone 4 110 ° g- zone 5 and 6 63 ° c

TDO screw speed, speed 160 / min. line speed 40 m / min

A coextruded film having a thickness of 0.032 mm propylene polymer mass according to Example 2, stabilized as shown in Example 3 but without Millad 3905 and propylene Moplen S38F homopolymer 19 with an MFR of 2.0 dg / min, is prepared by extrusion of a three-layer laminate with biaxial orientation, as mentioned above. The properties of the thus obtained vil are shown in the following Table IV.

Table IV Lines Vagency Example 2 Coex ^ pp2 Yield Strength / MD / CD3 /, MPa 69.02 / 41.40 140.76 / 48.20 154.0 / 70.0 Tensile Strength / MD / CD / MPa 67.76 / 41.12 140.76 / 41.20 154.0 / 70.0 Relative elongation at flow / MD / CD /,% 6/25 11/16 7/30 Relative elongation at. break / MD / CD /%. 6/25 11/16 7/30 Bursting Elemen-dorf / MD / CD / g / ply 7/5 5/5 4/5 Turbidity 0.1 1.0 Gloss 95 90 85 Part. friction / static / kinetic without slip 1,4 / 0,88 - Permeability, for water steam at 38 QC and 100% relative humidity / 645 cm2 / 24 h 0,580 0,355 0,40 Impact, J 2,23 3,17 - Shrinkage / MD / CD / at. 100 ° CL 20/30 3/3 - at. 120 ° C 60/75 8/12 -

1 propylene polymer mass according to Example 2 / homopolymer propylene / propylene. the polymer mass of Example 2 wherein the co-extruded film has S.I.T. 105 ° C - 20 ° C

a propylene Hoplen S38F MFR of 2.0 dg / min and a SIT of approximately 163 ° C of Table IV shows that the propylene polymer mass of the invention provides a biaxial oriented film with improved SIT, improved Slemendorf tear characteristics, less lean and more gloss and better overall balanced features. Various types of film materials of conventional thickness and thin film thicknesses of less than 0.508 mm to 0.0127 mm can be prepared using the inventive propylene polymer composition and also heavier film materials, generally referred to as 0.508 to 2.540 mm sheets. For example, in addition to the above examples, it can be used to produce uniaxially oriented films and extruded or calendered sheets. In addition, the layer containing the propylene polymer may be applied, for example, by lamination or co-extrusion. on at least one surface of the thermoplastic film material or on a metal sheet or foil substrate. Typical thermoplastic materials include crystalline homopolymers of alpha-olefin monomers and from 2 to 10 carbon atoms, such as propylene or ethylene or copolymers of propylene with ethylene / or carbon with an alpha-olefin monomer having from 4 to 10 carbon atoms. the olefin monomer is ethylene, the maximum content of polymerized ethylene is about 10%, preferably about 4%, and if the alpha-olefin is an olefin having 4 to 10 carbon atoms, the maximum polymer content is about 20%, preferably about 16%, and also polyesters, polyamides, ethylene vinyl alcohol copolymers and ethylene vinyl acetate copolymers. Aluminum is a suitable metal substrate.

In addition, the films may be prepared from mixtures of about 5 to 45% by weight of the propylene polymer composition of the present invention with about 95 to 55% of a crystalline alpha-olefin monomer homopolymer; with 2 to 10 carbon atoms or a copolymer of propylene with ethylene and / or an alpha-olefin monomer with 4 to 10 carbon atoms as mentioned above. Preferably, the amount of propylene polymer composition contained in such compositions is 21 to 10% by weight. The inventive propylene polymer material is a finished product-weighted material wherein its film layer is a material deposited on at least one surface of another thermoplastic material or onto a metal substrate and blends with another thermoplastic material. uses such mixtures for making films.

Propylene polymer film and film laminates have at least one layer of films prepared from their mixtures with other thermoplastic materials and can be used for packaging purposes, in the manufacture of chemical and hazardous waste packaging, and for medical use. The term "consisting essentially of" used in the description of the exemplified compound in concentrations sufficient to substantially adversely affect the important properties and characteristics of the defined compositions of the invention, while allowing the presence of one or more of the unspecified substances at the inadequate concentrations of the essential adverse characteristics.

Other characteristics, advantages and embodiments of the invention will be apparent to those skilled in the art. Thus, while specific specific embodiments are described, variations and modifications of the invention are possible within its protected scope.

Industrial usability

A crystalline propylene polymer-based film and sheet mold suitable for packaging food, chemicals, hazardous wastes and medical purposes, showing good weld strength.

Claims (7)

22 CJ «PATENTOVI A film or sheet material comprising a crystalline propylene polymer mass comprising from about 30% to about 65% by weight of propylene copolymer with an alpha-olefin having from 4 to 8 carbon atoms, containing from about 80% to about 98% propylene a / B (35 to 70% of a copolymer consisting essentially of propylene with ethylene having an ethylene content of 5 to 10%). Film or sheet material according to claim 1, characterized in that the component (A) is a copolymer of propylene and butene-1. 3. Film or sheet material according to claim 1, characterized in that the component (A) is present in a weight ratio of 35 to 65% and the component (B) is present in a quantity of 35 to 65% by weight. Film or sheet material according to claim 1, characterized in that the component (A) is present in a weight ratio of 45 to 65% and the component (B) is present in a weight ratio of 35 to 55% A film or sheet comprising a base film or sheet of a crystalline homopolymer of a C 2 -C 10 alpha-olefin or copolymer of propylene with ethylene or a copolymer of propylene with an alpha-olefin monomer of 4 to 10 carbon atoms, or of a propylene copolymer with 4 to 10 carbon atoms with an alpha-olefin, the copolymer being a copolymer with ethylene, a maximum polymerized ethylene content of about 10% and a copolymer with an alpha-olefin having 4 to 10 atoms carbon. the maximum polymer content thereof is about 20%, wherein a layer of material according to claim 1, 2 or 3 is deposited on at least one surface of the base film or sheet. 6. A film or sheet product, characterized in that the base film or sheet of metal substrate has a material according to claim 1, 2 or 3 deposited on at least one surface. A film or sheet material comprising from 1 to 5 to 45% by weight of a crystalline propylene polymer mass which contains from 30 to 65% by weight of copolymer of propylene with an alpha-olefin of from 4 to 8 carbon atoms; containing from 80 to 98% by weight of propylene and / B / from 35 to 70% of a copolymer consisting essentially of propylene with ethylene having an ethylene content of 5 to 10% a / 2 / about 95 to 55% of a crystalline homopolymer of alpha-olefin monomer with 2 to 10 carbon atoms or a copolymer of propylene with ethylene or a copolymer of propylene with an alpha-olefin monomer having 4 to 10 carbon atoms, or a copolymer of propylene with ethylene and an alpha-olefin with 4 to 10 carbon atoms, provided that the copolymer is a copolymer with ethylene, wherein the maximum ethylene content of the polymerized material is 10%, and if the copolymer is a copolymer with an alpha-olefin, and 4 to 10 carbon atoms, the maximum polymer content is 20%, 8%, or sheets. characterized in that it comprises a crystalline polymeric propylene mass which contains from 45 to 65% by weight / copolymer of propylene with an alpha-olefin of 4 to 8 carbon atoms containing 80 to 98% propylene and / B / 35 by weight. up to 55% of a propylene-ethylene terpolymer with an alpha-olefin of 4 to 8 carbon atoms having an ethylene content of 0.5 to 5%, an alpha-olefin content of 4 to 8 carbon atoms, with a total ethylene content of 1 to 9.5% and a 4 to 8 carbon alpha-olefin is 2 to 10% · 9. Film or sheet material comprising a mixture by weight / 1/5 to 45% of a crystalline propylene polymer composition according to claim 8 a / 2/95 to 55% of a crystalline 2-a-olefin monomer homopolymer. 10 10 carbon atoms or a propylene copolymer with ethylene or a copolymer of propylene with an alpha-olefin monomer having from 4 to 10 carbon atoms or a copolymer of ethylene and alpha-olefin having from 4 to 10 carbon atoms, provided that the copolymer is copolymerized with ethylene; ethylene is 10%, and when the copolymer is a copolymer with an alpha-olefin having from 4 to 10 carbon atoms, the polymer content is at most 20%. 10. A film or sheet product comprising a base film or a crystalline sheet. a homopolymer of an alpha-olefin monomer having 2 to 10 carbon atoms, or a co-polymer of propylene with ethylene or a copolymer of propylene with ethylene and an alpha-olefin of 4 to 10 at with the proviso that in the case where the copolymer is a copolymer with ethylene, the maximum content of ethylene polymerized is 10% and, in the case where the copolymer is a copolymer with an alpha-olefin of 4 to 10 carbon atoms, the maximum content of this polymer is 20%; at least one film of sheet or sheet is a material according to claim 8. 11 A film or sheet product, wherein the base film or sheet of metal substrate is coated on at least one surface with a layer of material according to claim 8.